CN101545076B - Martensite refractory stainless steel and manufacturing method thereof - Google Patents
Martensite refractory stainless steel and manufacturing method thereof Download PDFInfo
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- CN101545076B CN101545076B CN2008100350565A CN200810035056A CN101545076B CN 101545076 B CN101545076 B CN 101545076B CN 2008100350565 A CN2008100350565 A CN 2008100350565A CN 200810035056 A CN200810035056 A CN 200810035056A CN 101545076 B CN101545076 B CN 101545076B
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Abstract
The invention provides a martensite refractory stainless steel and a manufacturing method thereof. The martensite refractory stainless steel comprises the following chemical compositions by weight percentage: 0.10 to 0.20 weight percent of C, less than or equal to 0.50 weight percent of Mn, less than or equal to 0.50 weight percent of Si, less than or equal to 0.030 weight percent of P, less than or equal to 0.015 weight percent of S, 10.00 to 13.00 weight percent of Cr, 1.50 to 2.50 weight percent of Ni, 0.60 to 1.00 weight percent of W, 1.30 to 1.70 weight percent of Mo, 0.15 to 0.30 weight percent of V, 0.20 to 0.40 weight percent of Nb, 0.02 to 0.12 weight percent of N, and the balance of Fe and inevitable impurities. A martensite stainless steel with strength and toughness matching, strong heat tolerance and corrosion resistance is manufactured by intensified vacuum smelting and forging technology. The martensite refractory stainless steel can work for a long time at high temperature of 650 DEG C, and can satisfy the using requirement of heat resistant critical components applied to steam turbines and combustion turbines.
Description
Technical field
The present invention relates to the heat-resistance stainless steel material type, specifically, the present invention relates to a kind of martensite refractory stainless steel and method of manufacture thereof.
Background technology
High temperature steel be meant at high temperature have sufficient intensity, the steel of certain oxidation-resistance and erosion resistance and secular structure stability.The development of high temperature steel is the needs of the power machine of work under the high temperature, like steam boiler, steam turbine, the reaction propulsion engine of aircraft industry and the hot operation parts of industrial sectors such as space flight, naval vessel, oil and chemical industry of thermal power plant.They at high temperature bear various load, as stretch, crooked, reverse, fatigue and impact etc., in addition, they also with high temperature, steam, air or contacts fuel gas, high temperature oxidation or gaseous corrosion take place in the surface.At high temperature work, the atomic diffusion process will take place in steel, and cause structural transformation, and Here it is and the difference of low-temperature working parts.Basic demand to high temperature steel is: the one, and the plasticity that have good high-temperature intensity and adapt with it; The 2nd, have sufficiently high chemicalstability, as anti-oxidant, anticorrosive etc.
High temperature steel comprises Refractory Steel and Oxidation Resistant Steel.Refractory Steel refers to the steel that at high temperature has sufficient intensity and certain oxidation-resistance is arranged, and rotor and blade, boiler superheater, the high temperature that is usually used in making turbine, internal combustion turbine is bolt and the spring etc. of work down.Refractory Steel commonly used has perlite Refractory Steel, martensite Refractory Steel and austenite Refractory Steel etc.For the martensite Refractory Steel, it is more that this type Refractory Steel contains alloying element, and using the widest is the Cr13 steel that contains chromium 13%; In order to improve heat resistance; Generally also add strengthening element tungsten, molybdenum, vanadium etc., like 1Cr12MoV, 1Cr12WMoV etc., their oxidation-resistance and weakening performance all are superior to the perlite Refractory Steel; Can be widely used in the turbine blade made below 600 ℃, eddy pressurizer blade, valve, main shaft etc.; Another kind of is the martensite Refractory Steel that contains chromium, silicon, like 4Cr9Si2,4Cr10Si2Mo etc., adds chromium and silicon and can improve oxidation-resistance and anti-burning smoke gas (comprising the leadization thing) corrosive performance; Mainly be used for making the engine exhaust valve, also can make 800 ℃ with less process furnace member of lower stress etc.
At present; Domesticly on heat-resisting (like withstand voltage high temperature resistant housing, wheel disc, blade, axle class, fastening piece etc.) composition design, quality level and production technology with material of turbine, internal combustion turbine and various movers, have certain problem: 1) there is defective in steel grades design; Such as not adding in this type of steel grade or adding very small amount strengthening element nitrogen, cause the temperature capacity of steel not enough.2) production process is lack of standardization, as adopts two vacuum metling technologies, need the overall chemical ingredients of control, has improved the performance quality that cost does not but improve steel, causes rolled steel market white war ability low.Associated class is seen table 1 like the chemical ingredients of Refractory Steel.
The chemical ingredients (wt%) of the existing Refractory Steel of table 1
| Steel grade | C | Mn | Si | P | S | Cr | Ni | W | Mo | V | Nb | N |
| 1Cr12Ni2W MoVNb | 0.11～ 0.17 | ≤ 0.60 | ≤ 0.60 | ≤ 0.030 | ≤ 0.025 | 11.00～ 12.00 | 1.80～ 2.20 | 0.70～ 1.00 | 0.80～ 1.20 | 0.20～ 0.30 | 0.15～ 0.30 | |
| 1Cr10Co6Ni MoNbN | 0.06～ 0.11 | 0.60～ 1.15 | 0.10～ 0.70 | ≤ 0.028 | ≤ 0.020 | 9.80～ 11.20 | 0.20～ 0.80 | Co5.0～ 7.00 | 0.50～ 1.00 | 0.10～ 0.35 | 0.20～ 0.45 | 0.010～ 0.035 |
| 1Cr10Co3W 2MoVNbN | 0.09～ 0.15 | ≤ 0.15 | ≤ 0.10 | ≤ 0.015 | ≤ 0.005 | 10.00～ 10.50 | Co3.0～ 3.50 | 2.50～ 2.90 | 0.65～ 0.75 | 0.15～ 0.25 | 0.06～ 0.15 | 0.010～ 0.035 |
Do not add strengthening element nitrogen in the chemical ingredients of steel grade 1Cr12Ni2WMoVN, cause the temperature capacity of steel not enough, the rate under 550 ℃, 325MPa, 100h condition is about 0.2%.Added the noble metal Co and the W element of more amount among steel grade 1Cr10Co6NiMoNbN and the steel grade 1Cr10Co3W2MoVNbN respectively,, increased production cost although Co can improve the creep strength of steel.
The present inventor is with raw material ratio cheaply, through strengthening vacuum metling and forging process, made a kind ofly have the obdurability coupling, temperature capacity is strong and erosion-resisting Martensite Stainless Steel, thereby accomplished the present invention.
One object of the present invention is to provide a kind of martensite refractory stainless steel.
Another object of the present invention is to provide the method for manufacture of said martensite refractory stainless steel.
Summary of the invention
First aspect of the present invention provides a kind of martensite refractory stainless steel; This stainless chemical ingredients comprises: C:0.10～0.20wt%, Mn≤0.50wt%, Si≤0.50wt%, P≤0.030wt%, S≤0.015wt%, Cr:10.00～13.00wt%, Ni:1.50～2.50wt%, W:0.60～1.00wt%, Mo:1.30～1.70wt%, V:0.15～0.30wt%, Nb:0.20～0.40wt%, N:0.02～0.12wt%, surplus is Fe and unavoidable impurities.
In a preferred implementation: the chemical ingredients of said martensite refractory stainless steel comprises: C:0.12～0.18wt%, Mn:0.35～0.45wt%, Si:0.35～0.45wt%, P≤0.020wt%, S≤0.015wt%, Cr:11.50～12.50wt%, Ni:1.80～2.20wt%, W:0.70～0.90wt%, Mo:1.40～1.70wt%, V:0.20～0.30wt%, Nb:0.25～0.30wt%, N:0.03～0.08wt%, surplus is Fe and unavoidable impurities.
Suitable carbon content and nitrogen content; Under the cooperation of other each element; The matrix that guarantees steel is single martensite, prevents that free ferrite from producing, and makes steel have certain intensity toughness and thermotolerance; In addition, the control carbon content is not wanted too high to alleviate anti-corrosion capability and the toughness generation detrimentally affect to steel as far as possible.Residual element such as sulphur, phosphorus, hydrogen, oxygen have detrimentally affect to plasticity, toughness, the especially thermal fatigue property of steel, so its content of control should be low as far as possible.Chromium is to guarantee that this steel has non-corrosive and corrosion resistance nature; Nickel element cooperates with carbon, nitrogen element with molybdenum element, W elements and vanadium, niobium element, main effect be steel in drawing process carbide precipitate, carbonitride second with the heat resistance of raising steel.Silicon, manganese element mainly are to keep being prone in the steel stability of scaling loss elemental niobium in reflow process.
Second aspect of the present invention provides a kind of martensite heat-flash stainless method of manufacture; This method of manufacture comprises smelting, cast, esr, heating, forging, annealing, modulation heat treatment step; Wherein said stainless chemical ingredients comprises: C:0.10～0.20wt%, Mn≤0.50wt%, Si≤0.50wt%, P≤0.030wt%, S≤0.015wt%, Cr:10.00～13.00wt%, Ni:1.50～2.50wt%, W:0.60～1.00wt%, Mo:1.30～1.70wt%, V:0.15～0.30wt%, Nb:0.20～0.40wt%, N:0.02～0.12wt%, surplus is Fe and unavoidable impurities.
In a preferred implementation: smelt and adopt vacuum induction furnace smelting.
In a preferred implementation: in said esr operation, molten speed is 390～420Kg/h, adopts CaF2, Al
2O
3, MgO ternary slag system control slag viscosity and potential of hydrogen, three's proportioning is 68～72: 23～27: 4～6.
In a preferred implementation: in said heating process, steel ingot is lower than 450 ℃ of heating, and the speed heating 14～19h with≤50 ℃/h is cooled to 1180 ± 20 ℃ of insulations 3 hours after 1200～1250 ℃ of homogenizing.
In a preferred implementation: in said forging process, steel billet 1.3～2h heat-up time, 1118～1136 ℃ of Heating temperatures, forging ratio are greater than 6, and the fire of becoming a useful person at last is controlled at 1120 ± 10 ℃, roll forming.
In a preferred implementation: in the said operation of rolling, 1115～1120 ℃ of Heating temperatures, heat-up time 0.9～1.3h, finishing temperature is greater than 800 ℃.
In a preferred implementation: said annealing temperature is 700～725 ℃, and annealing time is 25～30h.
One preferred embodiment in: in said modified heat treatment step, forging is in 1120 ± 10 ℃ of quenchings, and insulation 1～3.5h oil cooling is to room temperature, and again in 680 ± 15 ℃ of tempering, insulation 2～4.5h air cooling is to room temperature.
In the stainless method of manufacture of martensite heat-flash of the present invention, following to the control analysis of master operation:
1, smelts
Adopt vacuum induction furnace smelting, omnidistance high vacuum is strengthened the degassing and is gone to be mingled with operation, guarantees that composition reaches evenly that foreign matter content is low, each constituent content meets the requirements.At first to select highly purified mother alloy, pure iron, iron alloy and pure metal starting material thereof, carry out melting by vacuum induction furnace smelting process curve shown in Figure 1 again.This technology highlights under the condition of high vacuum degree smelts the sufficiently long time, to guarantee to remove gas and detrimental impurity element thereof.
2, esr
Should control molten speed 390～420Kg/h, adopt rare gas element Ar protection, it is oxidized to alleviate molten steel, CaF
2: Al
2O
3: the viscosity and the potential of hydrogen of MgO ternary slag system control slag.Whole-process automatic control guarantees that steel ingot has good crystalline state and surface quality, and detrimental impurity elements such as large-sized inclusions, sulphur are removed in wash heat simultaneously.
3, heating, forging
The preceding employing heating of forging is handled with homogenizing and is combined, forging rolling heat integration (or half heat integration) processing and forming technology; Forging ratio is greater than 6; With the meticulous of the inherent weave construction of steel with evenly guarantee that the metallurgical quality of steel is good, the extreme trace roll forming is with the high precision of assurance forging ' s block dimension.
Steel ingot after 1200～1250 ℃ of homogeneous heatingization, reduce to 1180 ± 20 ℃ the insulation 3 hours, with guarantee the burning, temperature is even, composition is even, plasticity-is in optimum regime.For making forging ratio greater than 6, carry out pier before becoming a useful person and forge the increase forging ratio, 1120 ± 10 ℃ of the fire time controls of becoming a useful person at last, roll forming, finishing temperature is greater than 800 ℃, and whole Zhi Yihuo completion is to keep its homogeneity.
4, modified thermal treatment
Forging must use after modified thermal treatment; Because it is extremely strong that martensite refractory stainless steel is stained with fire crack line susceptibility; Handle that the operation of each link is careless slightly can crackle to be taken place and scrap; Therefore qualified in order to guarantee the steel physicochemical property, avoid the generation of crackle waste product simultaneously, slowly quenching is the gordian technique of avoiding crackle to take place.Forging not speed limit is warming up to 1120 ± 10 ℃, is incubated 1～3.5 hour oil cooling of coming out of the stove to room temperature, is warming up to 680 ± 15 ℃ with 50 ℃ speed per hour then, is incubated 2～4.5 hours, and the air cooling of coming out of the stove is to room temperature.
Beneficial effect of the present invention is:
1, steel grade of the present invention is with raw material ratio cheaply; Substituted the expensive raw material ratios of noble metal such as containing high cobalt, high tungsten; The similar steel grade costs such as 1Cr10Co6NiMoNbN, 1Cr16Co5Ni2Mo2WVNbN, 1Cr11Co3W3NiMoVNbNB of comparing low about 40%; And 680 ℃ of use temperatures are suitable with this type steel grade, reached the limit of martensite refractory stainless steel use heat resisting temperature, improved the cost performance of this steel grade greatly.
2, the stainless clarity of the present invention, the degree that homogenizes are considerably beyond request for utilization; For prolonging steel guarantee is provided work-ing life; Its corrosion resistance, temperature capacity are stronger; Can restrain oneself under 650 ℃ of hot environments working long hours, satisfy the request for utilization of turbine, internal combustion turbine with heat-resisting key part.
Description of drawings
Fig. 1 is the vacuum induction furnace smelting process curve of martensite refractory stainless steel of the present invention.Among the figure, a section is the adjustment composition, and the b section is charged cast.
Embodiment
Below combine accompanying drawing that the present invention is made more detailed description with embodiment.These embodiment only are the descriptions to best mode for carrying out the invention, scope of the present invention are not had any restriction.
Embodiment 1
Chemical ingredients by shown in the table 2 is smelted in vacuum induction furnace, and its technical process is as shown in Figure 1, cast back esr, control CaF
2: Al
2O
3: MgO ternary slag system ratio, the processing parameter of smelting and esr is seen table 3.Steel ingot is lower than 450 ℃ and advances process furnace, and the speed heating 15h with≤50 ℃/h is cooled to 1160 ℃ after 1200～1250 ℃ of homogenizing, is incubated to begin after 3 hours to forge.Steel billet Forge Heating time 2h, 1120 ℃ of Heating temperatures, forging ratio be greater than 6, the fire of becoming a useful person at last is controlled at 1120 ± 10 ℃, 1120 ℃ of rolling Heating temperatures, heat-up time 1h, finishing temperature is greater than 800 ℃.Forging is in 720 ℃ of annealing, and annealing time is 30h, and or else speed limit is warming up to 1120 ℃ of quenchings, and insulation 2h comes out of the stove oil cooling to room temperature, is warming up to 680 ℃ of tempering with 50 ℃/h then, and insulation 4h comes out of the stove air cooling to room temperature.
Chemical ingredients by shown in the table 2 is smelted in vacuum induction furnace, and the processing parameter of smelting and esr is seen table 3.Steel ingot is lower than 450 ℃ and advances process furnace, and the speed heating 16h with≤50 ℃/h is cooled to 1180 ℃ after 1200～1250 ℃ of homogenizing, is incubated to begin after 3 hours to forge.Steel billet Forge Heating time 1.5h, 1130 ℃ of Heating temperatures, forging ratio be greater than 6, the fire of becoming a useful person at last is controlled at 1120 ± 10 ℃, 1118 ℃ of rolling Heating temperatures, heat-up time 1.1h, finishing temperature is greater than 800 ℃.Forging annealing, quenching-and-tempering process parameter are seen table 4.All the other embodiments are with embodiment 1.
Chemical ingredients by shown in the table 2 is smelted in vacuum induction furnace, and the processing parameter of smelting and esr is seen table 3.Steel ingot is lower than 450 ℃ and advances process furnace, and the speed heating 14h with≤50 ℃/h is cooled to 1190 ℃ after 1200～1250 ℃ of homogenizing, is incubated to begin after 3 hours to forge.Steel billet Forge Heating time 1.8h, 1136 ℃ of Heating temperatures, forging ratio be greater than 6, the fire of becoming a useful person at last is controlled at 1120 ± 10 ℃, 1116 ℃ of rolling Heating temperatures, heat-up time 1.3h, finishing temperature is greater than 800 ℃.Forging annealing, quenching-and-tempering process parameter are seen table 4.All the other embodiments are with embodiment 1.
Embodiment 4
Chemical ingredients by shown in the table 2 is smelted in vacuum induction furnace, and the processing parameter of smelting and esr is seen table 3.Steel ingot is lower than 450 ℃ and advances process furnace, and the speed heating 17h with≤50 ℃/h is cooled to 1175 ℃ after 1200～1250 ℃ of homogenizing, is incubated to begin after 3 hours to forge.Steel billet Forge Heating time 1.6h, 1123 ℃ of Heating temperatures, forging ratio be greater than 6, the fire of becoming a useful person at last is controlled at 1120 ± 10 ℃, 1117 ℃ of rolling Heating temperatures, heat-up time 0.95h, finishing temperature is greater than 800 ℃.Forging annealing, quenching-and-tempering process parameter are seen table 4.All the other embodiments are with embodiment 1.
Chemical ingredients by shown in the table 2 is smelted in vacuum induction furnace, and the processing parameter of smelting and esr is seen table 3.Steel ingot is lower than 450 ℃ and advances process furnace, and the speed heating 19h with≤50 ℃/h is cooled to 1165 ℃ after 1200～1250 ℃ of homogenizing, is incubated to begin after 3 hours to forge.Steel billet Forge Heating time 1.3h, 1118 ℃ of Heating temperatures, forging ratio be greater than 6, the fire of becoming a useful person at last is controlled at 1120 ± 10 ℃, 1115 ℃ of rolling Heating temperatures, heat-up time 1.2h, finishing temperature is greater than 800 ℃.Forging annealing, quenching-and-tempering process parameter are seen table 4.All the other embodiments are with embodiment 1.
The chemical ingredients (wt%) of table 2 embodiment of the invention 1-5 martensite refractory stainless steel
| Element | C | Mn | Si | P | S | Cr | Ni | W | Mo | V | Nb | N |
| Embodiment 1 | 0.15 | 0.35 | 0.41 | 0.007 | 0.005 | 10.05 | 1.60 | 0.70 | 1.52 | 0.26 | 0.28 | 0.032 |
| Embodiment 2 | 0.18 | 0.37 | 0.40 | 0.012 | 0.002 | 11.89 | 1.91 | 0.88 | 1.49 | 0.24 | 0.27 | 0.078 |
| Embodiment 3 | 0.17 | 0.41 | 0.35 | 0.007 | 0.003 | 12.02 | 2.18 | 0.90 | 1.62 | 0.26 | 0.24 | 0.065 |
| Embodiment 4 | 0.16 | 0.38 | 0.40 | 0.010 | 0.006 | 11.69 | 1.98 | 0.89 | 1.42 | 0.21 | 0.29 | 0.058 |
| Embodiment 5 | 0.12 | 0.45 | 0.45 | 0.011 | 0.001 | 12.50 | 1.82 | 0.90 | 1.70 | 0.30 | 0.23 | 0.046 |
The smelting of table 3 embodiment of the invention 1-5 martensite refractory stainless steel and the processing parameter of esr
| Processing parameter | Vacuum time | Vacuum tightness | Refining time | Tapping temperature | Remelt speed | Slag system proportioning (CaF 2∶Al 2O 3∶MgO) |
| Embodiment 1 | 100% whole process | 2.7Pa | 45min | 1580℃ | 400Kg/h | 70∶25∶5 |
| |
80% whole process | 2.5Pa | 42min | 1570℃ | 420Kg/h | 72∶23∶5 |
| |
90% whole process | 2.6Pa | 55min | 1583℃ | 410Kg/h | 71∶25∶4 |
| Embodiment 4 | 65% whole process | 2.7Pa | 48min | 1578℃ | 400Kg/h | 70∶24∶6 |
| |
60% whole process | 2.4Pa | 50min | 1582℃ | 390Kg/h | 68∶27∶5 |
Annealing, the quenching-and-tempering process parameter of table 4 embodiment of the invention 1-5 martensite refractory stainless steel
| Processing parameter | Annealing temperature (℃) | Annealing time (h) | Quenching temperature (℃) | Cool time (h) | Tempering temperature (℃) | Tempering time (H) |
| Embodiment 1 | 720 | 30 | 1120 | 2.8 | 680 | 4.0 |
| |
725 | 25 | 1124 | 1.5 | 690 | 3.2 |
| |
715 | 28 | 1125 | 1.8 | 685 | 3.5 |
| Embodiment 4 | 700 | 30 | 1110 | 2.7 | 670 | 4.2 |
| |
723 | 27 | 1119 | 2.2 | 672 | 4.9 |
Test Example 1
Martensite refractory stainless steel to embodiment of the invention 1-5 is carried out Mechanics Performance Testing, and test result is seen table 5.
The mechanical property of the martensite refractory stainless steel of table 5 embodiment of the invention 1-5
| Project | Ys Rm (MPa) | Tensile strength Rp0.2 (MPa) | Unit elongation A (%) | Relative reduction in area Z (%) | Impelling strength AKu (J) | HB HB | 550 ℃, 325MPa, 100h rate (%) |
| Embodiment 1 | 1090 1120 | 925 930 | 17 17 | 59 60 | 64 67 | 305 312 | 0.12 |
| |
1080 1100 | 935 940 | 16 18 | 58 60 | 66 70 | 305 321 | 0.11 |
| |
1085 1130 | 940 955 | 17 18 | 57 62 | 67 69 | 321 325 | 0.10 |
| Embodiment 4 | 1090 1100 | 925 930 | 17 17 | 57 60 | 64 71 | 325 332 | 0.12 |
| |
1090 1110 | 905 925 | 18 19 | 56 58 | 52 55 | 305 312 | 0.10 |
Test Example 2
The martensite refractory stainless steel of embodiment of the invention 1-5 is carried out macroscopic view, micro-quality inspection statistics, and statistics is seen table 6.
The martensite refractory stainless steel macroscopic view of table 6 embodiment of the invention 1-5, micro-quality inspection statistics
Claims (9)
1. the method for manufacture of a martensite refractory stainless steel; This method of manufacture comprises smelting, cast, esr, heating, forging, annealing, modified heat treatment step; It is characterized in that; Said stainless chemical ingredients comprises: C:0.10～0.20wt%, Mn≤0.50wt%, Si≤0.50wt%, P≤0.030wt%, S≤0.015wt%, Cr:10.00～13.00wt%, Ni:1.50～2.50wt%, W:0.60～1.00wt%, Mo:1.30～1.70wt%, V:0.15～0.30wt%, Nb:0.20～0.40wt%, N:0.02～0.12wt%, and surplus is Fe and unavoidable impurities; In said esr operation, molten speed is 390～420Kg/h, adopts CaF
2, Al
2O
3, MgO ternary slag system control slag viscosity and potential of hydrogen, three's proportioning is 68～72: 23～27: 4～6.
2. method of manufacture according to claim 1, vacuum induction furnace smelting is adopted in said smelting.
3. method of manufacture according to claim 1, in said heating process, steel ingot is lower than 450 ℃ of heating, and the speed heating 14～19h with≤50 ℃/h is cooled to 1180 ± 20 ℃ of insulations 3 hours after 1200～1250 ℃ of homogenizing.
4. method of manufacture according to claim 1, in said forging process, steel billet 1.3～2h heat-up time, 1118～1136 ℃ of Heating temperatures, forging ratio are greater than 6, and the fire of becoming a useful person at last is controlled at 1120 ± 10 ℃, roll forming.
5. method of manufacture according to claim 4, in the said operation of rolling, 1115～1120 ℃ of Heating temperatures, heat-up time 0.9～1.3h, finishing temperature is greater than 800 ℃.
6. method of manufacture according to claim 1, said annealing temperature are 700～725 ℃, and annealing time is 25～30h.
7. method of manufacture according to claim 1, in said modified heat treatment step, forging is in 1120 ± 10 ℃ of quenchings, and insulation 1～3.5h oil cooling is to room temperature, and again in 680 ± 15 ℃ of tempering, insulation 2～4.5h air cooling is to room temperature.
8. martensite refractory stainless steel of processing with the said method of manufacture of claim 1; It is characterized in that; 1) chemical ingredients of said martensite refractory stainless steel comprises: C:0.10～0.20wt%, Mn≤0.50wt%, Si≤0.50wt%, P≤0.030wt%, S≤0.015wt%, Cr:10.00～13.00wt%, Ni:1.50～2.50wt%, W:0.60～1.00wt%, Mo:1.30～1.70wt%, V:0.15～0.30wt%, Nb:0.20～0.40wt%, N:0.02～0.12wt%, and surplus is Fe and unavoidable impurities; 2) said stainless steel adopts electroslag remelting process, and in said esr operation, molten speed is 390～420Kg/h, adopts CaF
2, Al
2O
3, MgO ternary slag system control slag viscosity and potential of hydrogen, three's proportioning is 68～72: 23～27: 4～6.
9. martensite refractory stainless steel according to claim 8; It is characterized in that; The chemical ingredients of said martensite refractory stainless steel comprises: C:0.12～0.18wt%, Mn:0.35～0.45wt%, Si:0.35～0.45wt%, P≤0.020wt%, S≤0.015wt%, Cr:11.50～12.50wt%, Ni:1.80～2.20wt%, W:0.70～0.90wt%, Mo:1.40～1.70wt%, V:0.20～0.30wt%, Nb:0.25～0.30wt%, N:0.03～0.08wt%, surplus is Fe and unavoidable impurities.
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